RoamingSettings only supports the runtime data types (with exception of Uri); additionally, there's a limitation as to how much data you can save per setting and in total.
You'd be better off using RoamingFolder (or perhaps LocalFolder) for the storage aspects.
For the serialization aspect you might try the DataContractSerializer. If you have a class like:
public class MyData
{
public int Prop1 { get; set; }
public int Prop2 { get; set; }
}
public ObservableCollection<MyData> coll;
then write as follows
var f = await Windows.Storage.ApplicationData.Current.LocalFolder.CreateFileAsync("data.txt");
using ( var st = await f.OpenStreamForWriteAsync())
{
var s = new DataContractSerializer(typeof(ObservableCollection<MyData>),
new Type[] { typeof(MyData) });
s.WriteObject(st, coll);
and read like this
using (var st = await Windows.Storage.ApplicationData.Current.LocalFolder.OpenStreamForReadAsync("data.txt"))
{
var t = new DataContractSerializer(typeof(ObservableCollection<MyData>),
new Type[] { typeof(MyData) });
var col2 = t.ReadObject(st) as ObservableCollection<MyData>;
}